JPH01233263A - Phenylbutadiyne derivative - Google Patents
Phenylbutadiyne derivativeInfo
- Publication number
- JPH01233263A JPH01233263A JP5870688A JP5870688A JPH01233263A JP H01233263 A JPH01233263 A JP H01233263A JP 5870688 A JP5870688 A JP 5870688A JP 5870688 A JP5870688 A JP 5870688A JP H01233263 A JPH01233263 A JP H01233263A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- solvent
- group
- expressed
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NQLJPVLOQMPBPE-UHFFFAOYSA-N buta-1,3-diynylbenzene Chemical class C#CC#CC1=CC=CC=C1 NQLJPVLOQMPBPE-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 17
- 230000003287 optical effect Effects 0.000 abstract description 14
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical compound C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 8
- PCIPCEOKFBAUNM-UHFFFAOYSA-N 4-bromo-2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#CBr PCIPCEOKFBAUNM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 52
- 239000002904 solvent Substances 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 14
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 12
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- -1 copper (1) ions Chemical class 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 description 1
- FWAGYANFBMIHFQ-UHFFFAOYSA-N 1-ethynyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C#C FWAGYANFBMIHFQ-UHFFFAOYSA-N 0.000 description 1
- JOUOQPWPDONKKS-UHFFFAOYSA-N 1-ethynyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C#C)=C1 JOUOQPWPDONKKS-UHFFFAOYSA-N 0.000 description 1
- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical compound NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 description 1
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XETHXRSXCFDQFV-UHFFFAOYSA-N hexa-3,5-diyn-2-ol Chemical compound CC(O)C#CC#C XETHXRSXCFDQFV-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
未発明はフェニルブタジイン誘導体、詳しくは固相重合
性を有し、且つ置換基がジアセチレン三重結合と共役す
るフェニルブタジイン誘導体に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to phenylbutadiyne derivatives, specifically phenylbutadiyne derivatives that have solid phase polymerizability and in which a substituent is conjugated with a diacetylene triple bond. be.
本発明に係るフェニルブタジイン誘導体は、固相重合性
を有することにより、非線形光学材料、感光材料及び高
分子半導体結晶として用いられる。The phenylbutadiyne derivative according to the present invention has solid phase polymerizability, and thus can be used as a nonlinear optical material, a photosensitive material, and a polymer semiconductor crystal.
近年、非線形光学材料、感光材料及び高分子半導体結晶
等を形成する為の単量体として、ジアセチレン類の研究
が盛んに行われている。In recent years, diacetylenes have been actively researched as monomers for forming nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, and the like.
非線形光学材料、感光材料及び高分子半導体結晶等を形
成する為には、ジアセチレン類の単量体が固相重合性を
有することが必要である。また、非線形光学材料として
、非線形光学効果の向上の為には、周知の通り、主鎖−
側鎖が共役していることによって、電子的効果の大きい
ことが必要である。In order to form nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, etc., it is necessary that diacetylene monomers have solid phase polymerizability. In addition, as a nonlinear optical material, in order to improve the nonlinear optical effect, it is necessary to
It is necessary that the side chain is conjugated to have a large electronic effect.
従来、−最大
％式％（１）
で表され・るジアセチレン類のうちい（つかの化合〔発
明が解決しようとする問題点〕
高い固相重合性を有し、置換基がジアセチレン三重結合
と共役する単量体は現在量も要求されているところであ
るが、前述した既知の固相重合性を有するジアセチレン
類は、−最大（１）で、Ｒａ−Ｒｂの様にジアセチレン
部分の両端に同一の置換基を有し、対称分子を形成して
いるために、偶数次の非線形光学効果がまったく期待で
きない。Conventionally, among the diacetylenes represented by the formula % (1) (some compounds [problems to be solved by the invention]) have high solid phase polymerizability and have a substituent group of diacetylene triple Although the amount of monomer conjugated with the bond is currently required, the above-mentioned known diacetylenes having solid phase polymerizability have a maximum of (1) and a diacetylene moiety such as Ra-Rb. Since it has the same substituent at both ends and forms a symmetric molecule, no even-order nonlinear optical effect can be expected at all.
しかも、置換基とジアセチレン部分との共役が切れた構
造のものが大半を占めている。この様に主鎖−側鎖の共
役が切れた重合物では置換基Ｒａ、Ｒｂの電子的効果が
ほとんどなくなってしまい、どんな置換基であっても類
似の性質を呈する傾向がある。Moreover, most of them have a structure in which the conjugation between the substituent and the diacetylene moiety is broken. In a polymer in which the main chain-side chain conjugation is broken in this way, the electronic effects of the substituents Ra and Rb are almost eliminated, and any substituents tend to exhibit similar properties.
これに対し、−最大（１）で表されるジアセチレン化合
物で置換基Ｒａ及びＲｂが芳香族であるような化合物は
、同式中の三重結合と共役する為、形成される結晶性高
分子は優れた電子的性質が期待されるが、この様なジア
セチレン類は大半が固相重合性を示さないものである。On the other hand, diacetylene compounds represented by -maximum (1) in which the substituents Ra and Rb are aromatic are conjugated with the triple bond in the formula, so the crystalline polymer formed are expected to have excellent electronic properties, but most of these diacetylenes do not exhibit solid phase polymerizability.
ジフェニルジアセチレンの２つのフェニル基の各オルト
又はメタ位にアセチルアミノ基を有するものや、同フェ
ニル基の、２．４−ｉ２，５−ｉ３゜６−の位置にトリ
フルオロメチル基を有するもの等、固相重合性を有する
ものも若干あるが、これらは、各々の分子が対称構造を
とっているため、偶数次の非線形光学効果は発現しない
。Diphenyl diacetylene with an acetylamino group at each ortho or meta position of the two phenyl groups, or a trifluoromethyl group at the 2,4-i2,5-i3゜6-position of the same phenyl group There are some compounds that have solid phase polymerizability, such as, but since each molecule of these has a symmetrical structure, even-order nonlinear optical effects do not occur.
上述した通り、固相重合性を有し、且つ、構造的に非対
称型であり、しかも、置換基がジアセチレン三重結合と
共役する芳香族であることによって電子的効果が大きい
ジアセチレン類単量体は、現在、最も要求されていると
ころである。As mentioned above, diacetylene monomers that have solid phase polymerizability, are structurally asymmetric, and have a large electronic effect because the substituent is an aromatic group conjugated with a diacetylene triple bond. The body is currently in the greatest need.
本発明者は、高い固相重合性を有し、且つ、構造的に非
対称型であり、しかも置換基がジアセチレン三重結合と
共役する芳香族であることによって電子的効果が大きい
ジアセチレン類単量体を得るべく種々検討を行った結果
、本発明に到達した但し、
で表されるフェニルブタジイン誘導体である。The present inventor has developed diacetylene monomers that have high solid phase polymerizability, are structurally asymmetric, and have a large electronic effect due to the fact that the substituent is an aromatic group conjugated with a diacetylene triple bond. As a result of various studies to obtain a phenylbutadiyne derivative, the present invention was achieved.
先ず、本発明において、最も重要な点は、本発明に係る
フェニルブタジイン誘導体が固相重合性を有することに
起因して、非線形光学材料、感光材料及び高分子半導体
結晶を形成することができ、また、置換基がジアセチレ
ン三重結合と共役する芳香族であることによって電子的
効果が大きいことに起因して非線形光学効果が大きい点
である。First of all, the most important point in the present invention is that the phenylbutadiyne derivative according to the present invention has solid phase polymerizability, so that nonlinear optical materials, photosensitive materials, and polymer semiconductor crystals can be formed. Furthermore, since the substituent is an aromatic group conjugated with a diacetylene triple bond, the electronic effect is large, and the nonlinear optical effect is large.
また、本発明に係るフェニルブタジイン誘導体は、電子
吸引性基であるニトロ基または電子供与性基であるアミ
ノ基を有していることにより分子の分極が大きく、その
結果木きな非線形光学効果が期待でき、非線形光学材料
としての応用に際して極めて有利なものである。In addition, the phenylbutadiine derivative according to the present invention has a nitro group that is an electron-withdrawing group or an amino group that is an electron-donating group, so that the molecular polarization is large, resulting in a nonlinear optical effect such as wood. This is expected to be extremely advantageous when applied as a nonlinear optical material.
次に、本発明に係るフェニルブタジイン誘導体の合成方
法について述べる。Next, a method for synthesizing a phenylbutadiine derivative according to the present invention will be described.
本発明に係る下記の一般式で表されるフェニルブタジイ
ン誘導体は、
但し、
１、；“、″１；
で表されるフェニルアセチレン誘導体と４−ブロモ−２
−メチル−３−ブチン−２−オールとを非対称カップリ
ング反応して得られたで表されるフエニルジアセチレン
誘導体を水酸化カリウム触媒を用いて脱アセトン反応さ
せることによって合成することができる。The phenylbutadiyne derivatives represented by the following general formula according to the present invention include, however, a phenylacetylene derivative represented by 1; ","1; and 4-bromo-2
-Methyl-3-butyn-2-ol can be synthesized by deacetonizing the phenyl diacetylene derivative represented by the asymmetric coupling reaction using a potassium hydroxide catalyst.
先の非対称カップリング反応は種々の反応条件下で行う
ことができるが、いずれの場合にも銅塩の触媒作用が必
要である。具体的には、フェニルアセチレン誘導体の溶
液にアミン水溶液と塩化銅（１）を加えた後、攪拌しな
から４−ブロモー２−メチル−３−ブチン−２−オール
をゆっくりと加えることによって、非対称カップリング
反応は進行する。The above asymmetric coupling reaction can be carried out under various reaction conditions, but in all cases requires the catalytic action of a copper salt. Specifically, after adding an amine aqueous solution and copper chloride (1) to a solution of a phenylacetylene derivative, 4-bromo-2-methyl-3-butyn-2-ol was slowly added without stirring, resulting in an asymmetric reaction. The coupling reaction proceeds.
この反応の溶媒としては、メタノール、エタノール、テ
トラハイドロフラン、ジメチルホルムアミド、ジメチル
アセトアミドなどの極性溶媒が好ましい。アミン水溶液
としては一般にエチルアミン水溶液が用いられるが、他
のアミン水溶液も用いることができる。塩化銅（Ｈはフ
ェニルアセチレン誘導体に対して１〜１００ ｍｏ１％
の範囲内で用いる。As the solvent for this reaction, polar solvents such as methanol, ethanol, tetrahydrofuran, dimethylformamide, and dimethylacetamide are preferred. Ethylamine aqueous solution is generally used as the amine aqueous solution, but other amine aqueous solutions can also be used. Copper chloride (H is 1 to 100 mol% relative to the phenylacetylene derivative)
Use within the range of.
この反応はアルゴン又は窒素等の不活性ガス雰囲気下、
０〜５０″Ｃの条件で行い、場合によっては銅（１）イ
オンの酸化を防止するために、ヒドロキシルアミン塩酸
塩を適量加えながら、数時間乃至１〜２日間攪拌を続け
ることによって行う。This reaction is carried out under an inert gas atmosphere such as argon or nitrogen.
The reaction is carried out under conditions of 0 to 50''C, and in some cases, stirring is continued for several hours to 1 to 2 days while adding an appropriate amount of hydroxylamine hydrochloride to prevent oxidation of copper (1) ions.
反応終了後、反応混合物から溶媒を留去し、希塩酸水溶
液により中和希釈し、エーテル、ベンゼン等の溶媒によ
り抽出する。この溶液に硫酸ナトリウム、硫酸マグネシ
ウム等の乾燥剤を加えて脱り、式（４）で表されるフエ
ニルジアセチレン誘導体が白色ないし淡黄色の結晶とし
て得られる。After the reaction is completed, the solvent is distilled off from the reaction mixture, the mixture is neutralized and diluted with a dilute aqueous hydrochloric acid solution, and extracted with a solvent such as ether or benzene. A desiccant such as sodium sulfate or magnesium sulfate is added to this solution to remove it, and the phenyl diacetylene derivative represented by formula (4) is obtained as white to pale yellow crystals.
次に、得られたフエニルジアセチレン誘導体をベンゼン
、ヘキサン等の溶媒に溶解し、水酸化カリウム又は水酸
化ナトリウムを触媒量加え１〜１０時間還流する。反応
溶液を水洗した後溶媒を留去し、次いで、シリカゲルカ
ラムクロマトグラフィーを用いて精製することにより、
−最大（２）で表されるフェニルブタジイン誘導体が白
色又は淡黄色結晶として得られる。Next, the obtained phenyl diacetylene derivative is dissolved in a solvent such as benzene or hexane, and a catalytic amount of potassium hydroxide or sodium hydroxide is added thereto and refluxed for 1 to 10 hours. By washing the reaction solution with water, distilling off the solvent, and then purifying using silica gel column chromatography,
- A phenylbutadiine derivative represented by maximum (2) is obtained as white or pale yellow crystals.
次に実施例により本発明の詳細な説明する。 Next, the present invention will be explained in detail with reference to Examples.
実施例Ｉ
Ａｒ雰囲気下、塩化銅（ｒ）１．８ｇをエチルアミン７
０％１ｒｔＡＷ ＋ｏｏＩｄ、に溶解し、ここに２−エ
チニルニトロベンゼン４．４ｇをテトラヒドロフラン５
０ｍ１に溶解したものを加え２０分間室温で攪拌する。Example I Under Ar atmosphere, 1.8 g of copper chloride (r) was mixed with ethylamine 7
0% 1rtAW +ooId, and 4.4 g of 2-ethynylnitrobenzene was dissolved in 5% tetrahydrofuran.
Add the solution dissolved in 0ml and stir at room temperature for 20 minutes.
ここに４−ブロモ−２−メチル−３−ブチン−２−オー
ル６゜０ｇをテトラヒドロフラン６０ｍ１に溶解したも
のを約２時間かけて滴下、以後３時間室温で攪拌する。A solution of 6.0 g of 4-bromo-2-methyl-3-butyn-2-ol dissolved in 60 ml of tetrahydrofuran was added dropwise over about 2 hours, followed by stirring at room temperature for 3 hours.
（途中、塩化１４（ＴＩ）の生成により溶液が緑色を呈
した場合、適量のヒドロキシルアミン塩酸塩を加え還元
する。）反応混合物から溶媒を留去し、】規定塩酸水溶
液２００＋＋ｆｆｉにより中和、希釈しベンゼン１５０
ａ＋１により３回抽出する。有機層を硫酸ナトリウムで
乾燥後、溶媒を留去し、シリカゲルカラムクロマトグラ
フィーによりベンゼンを展開溶媒として分離、精製する
ことにより６−（２−ニトロフェニル）−２−メチル−
３，５−へキサジイン−２−オール２．８ｇを得た。こ
のものは白色結晶であった。(If the solution turns green due to the formation of 14 chloride (TI) during the process, add an appropriate amount of hydroxylamine hydrochloride for reduction.) The solvent is distilled off from the reaction mixture, and neutralized and diluted with a normal aqueous solution of hydrochloric acid 200++ffi. benzene 150
Extract 3 times with a+1. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 6-(2-nitrophenyl)-2-methyl- was separated and purified by silica gel column chromatography using benzene as a developing solvent.
2.8 g of 3,5-hexadiyn-2-ol was obtained. This substance was a white crystal.
次に得られたジアセチレン化合物２．５ｇをベンゼン１
００ｍｆｆ１に溶解し、ここに水酸化カリウム粉末０゜
６ｇを加え、０．５時間還流した。室温まで放冷した後
、１００ｄの水で水洗し、有機層を硫酸マグネシウムで
乾燥した後、溶媒を留去、シリカゲルカラムクロマトグ
ラフィーによりベンゼン、ヘキサン混合溶媒で展開し精
製することにより、１−（２−ニトロフェニル）ブタジ
イン１．２ｇを得た。このものは淡黄色結晶であった。Next, 2.5 g of the obtained diacetylene compound was added to 1 part of benzene.
0.00 mff1, 0.6 g of potassium hydroxide powder was added thereto, and the mixture was refluxed for 0.5 hour. After cooling to room temperature, the organic layer was washed with 100 d of water, dried over magnesium sulfate, the solvent was distilled off, and purified by silica gel column chromatography developed with a mixed solvent of benzene and hexane. 1.2 g of 2-nitrophenyl)butadiine was obtained. This substance was pale yellow crystal.
ｍ１１２４°Ｃ
元素分析値（Ｃ＋ｏ）ＩｓＮＯｚとして）計算値（χ’
）： Ｃ７０，１Ｂ、 Ｈ２，９４，Ｎ ８．１Ｂ実測
値（χ）； Ｃ７０，２５，Ｈ３，０１，Ｎ ８．．３
３実施例２
Ａｒ雰囲気下、塩化銅（１）２．１ｇをエチルアミン７
０％水溶液１００ｍｆｆ１に溶解し、ここに３−エチニ
ルニトロベンゼン４．１ｇをテトラヒドロフラン５０ａ
ｌｌに溶解したものを加え３０分間室温で撹拌する。こ
こに４−ブロモ−２−メチル−３−ブチン−２−オール
５゜５Ｂをテトラヒドロフラン６０ｄに溶解したものを
約２時間かけて滴下、以後３時間室温で攪拌する。m1124°C Elemental analysis value (C+o)IsNOz) Calculated value (χ'
): C70,1B, H2,94,N 8.1B actual value (χ); C70,25,H3,01,N 8. ．． 3
3 Example 2 Under Ar atmosphere, 2.1 g of copper chloride (1) was mixed with ethylamine 7
Dissolved in 100mff1 of 0% aqueous solution, 4.1g of 3-ethynylnitrobenzene was added to 50a of tetrahydrofuran.
Add the solution dissolved in 1 ml and stir at room temperature for 30 minutes. A solution of 4-bromo-2-methyl-3-butyn-2-ol 5.5B dissolved in 60 d of tetrahydrofuran was added dropwise over about 2 hours, followed by stirring at room temperature for 3 hours.
（途中、塩化銅（１）の生、成により溶液が緑色を呈し
た場合、適量のヒドロキシルアミン塩酸塩を加え還元す
る。）反応混合物から溶媒を留去し、１規定塩酸水溶液
１５０ｄにより中和、希釈しベンゼン１００−により３
回抽出する。有機層を硫酸ナトリウムで乾燥後、溶媒を
留去し、シリカゲルカラムクロマトグラフィーによりベ
ンゼンを展開溶媒として分離、精製することにより６−
（３−二トロフェニル）−２−メチル−３，５−へキサ
ジイン−２−オール４．２ｇを得た。このものは白色結
晶であった。(If the solution turns green due to the formation of copper chloride (1) during the process, add an appropriate amount of hydroxylamine hydrochloride and reduce.) The solvent is distilled off from the reaction mixture and neutralized with 150 d of 1N aqueous hydrochloric acid. , diluted with benzene 100-3
Extract times. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 6-
4.2 g of (3-nitrophenyl)-2-methyl-3,5-hexadiyn-2-ol was obtained. This substance was a white crystal.
次に得られたジアセチレン化合物４．２ｇをベンゼン１
５０ｍ１に溶解し、ここに水酸化カリウム粉末０゜８ｇ
を加え、２時間還流した。室温まで放冷した後、２００
ａ＋ｆｆｉの水で水洗し、有機層を硫酸マグネジウドで
乾燥した後、溶媒を留去、シリカゲルカラムクロマトグ
ラフィーによりベンゼン、ヘキサン混合溶媒で展開し精
製することにより、１−（３−ニトロフェニル）ブタジ
イン１．４ｇを得た。このものは白色結晶であった。Next, 4.2 g of the obtained diacetylene compound was added to 1 part of benzene.
Dissolve in 50ml and add 0゜8g of potassium hydroxide powder to it.
was added and refluxed for 2 hours. After cooling to room temperature, 200
After washing with water of a+ffi and drying the organic layer with magnesium sulfate, the solvent was distilled off, and 1-(3-nitrophenyl)butadiin 1 was purified by silica gel column chromatography developed with a mixed solvent of benzene and hexane. .4g was obtained. This substance was a white crystal.
融点 ９８°Ｃ
元素分析値（Ｃ＋。ＨｓＮＯｔとして）計算値（χ）；
Ｃ７０，１８，Ｉｔ ２．９４． Ｎ ８．１Ｂ実１
ｌｌｌ！ｌ値（χ）； Ｃ７０，２９，Ｉｔ ３．７５
． Ｎ ８．０２実施例３
Ａｒ雰囲気下、塩化銅（Ｔ）２．７ｇをエチルアミン７
０％水溶液１５０戚に溶解し、ここに２−エチニルアニ
リン３．１ｇをテトラヒドロフラン５０−に溶解したも
ｐ牽、加え６０分間室温で攪拌する。ここに４＝７・：
・ｋ・
ブ遺壬゛・−プ２−メチルー３−ブチシー２−オール５
．Ｏｇをテトラヒドロフラン４０ｍに溶解したものを約
２時間かけて滴下、以後３時間室温で攪拌する。（途中
、塩化銅（ＴＩ）の生成により溶液が緑色を呈した場合
、適量のヒドロキシルアミン塩酸塩を加え還元する。）
反応混合物から溶媒を留去し、水２００ｄにより希釈し
ベンゼン１５０＋ｆｆｉにより３回抽出する。有機層を
硫酸ナトリウムで乾燥後、溶媒を留去し、シリカゲルカ
ラムクロマトグラフィーによりベンゼンを展開溶媒とし
て分離、精製することにより６−（２−アミノフェニル
）−２−メチル−３，５−ヘキサシインー２−オール４
．９ｇを得た。このものは白色結晶であった。Melting point 98°C Elemental analysis value (C+. as HsNOt) Calculated value (χ);
C70,18,It 2.94. N 8.1B real 1
llll! l value (χ); C70, 29, It 3.75
．． N 8.02 Example 3 Under Ar atmosphere, 2.7 g of copper chloride (T) was mixed with ethylamine 7
A solution of 3.1 g of 2-ethynylaniline dissolved in 50% of tetrahydrofuran was added to the solution and stirred at room temperature for 60 minutes. Here 4=7・：
・k.
．． A solution of Og dissolved in 40 ml of tetrahydrofuran was added dropwise over about 2 hours, followed by stirring at room temperature for 3 hours. (During the process, if the solution turns green due to the formation of copper chloride (TI), add an appropriate amount of hydroxylamine hydrochloride for reduction.)
The reaction mixture is evaporated of the solvent, diluted with 200 d of water and extracted three times with 150 d of benzene+ffi. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 6-(2-aminophenyl)-2-methyl-3,5-hexacyin-2 was obtained by separating and purifying it by silica gel column chromatography using benzene as a developing solvent. -all 4
．． 9g was obtained. This substance was a white crystal.
次に得られたジアセチレン化合物３．２ｇをベンゼン１
００−に溶解し、ここに水酸化カリウ１１粉末０．４ｇ
を加え、０．５時間還流した。室温まで放冷した後、１
００ｄの水で水洗し、有機層を硫酸マグネシウムで乾燥
した後、溶媒を留去、シリカゲルカラ１１クロマトグラ
フイーによりベンゼン、ヘキサン混合溶媒で展開し精製
することにより、１−（２−アミノフェニル）ブタジイ
ン１．３ｇを得た。Next, 3.2 g of the obtained diacetylene compound was added to 1 part of benzene.
00-, and add 0.4g of potassium hydroxide 11 powder to it.
was added and refluxed for 0.5 hour. After cooling to room temperature, 1
After washing with 00d water and drying the organic layer with magnesium sulfate, the solvent was distilled off, and 1-(2-aminophenyl) was purified by silica gel color 11 chromatography developed with a mixed solvent of benzene and hexane. 1.3 g of butadiin was obtained.
このものは白色結晶であった。This substance was a white crystal.
融点 ５５℃
元素分析値（Ｃ＋。Ｉｔ、Ｎとして）
計算値（χ）； ＣＦ１５．０８． Ｉｔ ５．００．
Ｎ ９．９２実測値（χ’）： Ｃ８５，２４，Ｈ５
，ＩＬ Ｎ ９．７８実施例４
Ａｒ雰囲気下、塩化銅（Ｔ）２．７ｇをエチルアミン７
０％水溶液１５０ｒｒｄｌに溶解し、ここに３−エチニ
ルアニリン３．１ｇをテトラヒドロフラン５０−に溶解
したものを加え６０分間室温で攪拌する。ここに４＝ブ
ロモ−２−メチル−３−ブチン−２−オール４．９ｇを
テトラヒドロフラン６０ｍに溶解したものを約２時間か
けて滴下、以後３時間室温で攪拌する。（途中、塩化銅
（ｎ）の生成により溶液が緑色を呈した場合、適￥のヒ
ドロキシルアミン塩酸塩を加え還元する。）反応混合物
から溶媒を留去し、水２００１ｄにより希釈しベンゼン
１００ｄにより３回抽出する。有機層を硫酸ナトリウム
で乾燥後、溶媒を留去し、り刀、・カゲルカラムクロマ
トグラフィーに１゛：・ｌ゛・、
とにより６−（３−アミノフェニル）−２−メチル−３
，５−ヘキサジイン−２−オール４．８ｇを得た。この
ものは白色結晶であった。Melting point 55°C Elemental analysis value (C+. It, N) Calculated value (χ); CF15.08. It 5.00.
N 9.92 Actual value (χ'): C85, 24, H5
, IL N 9.78 Example 4 Under an Ar atmosphere, 2.7 g of copper chloride (T) was mixed with ethylamine 7
Dissolve in 150 rrdl of 0% aqueous solution, add thereto 3.1 g of 3-ethynylaniline dissolved in 50 ml of tetrahydrofuran, and stir at room temperature for 60 minutes. A solution of 4.9 g of 4=bromo-2-methyl-3-butyn-2-ol dissolved in 60 ml of tetrahydrofuran was added dropwise over about 2 hours, followed by stirring at room temperature for 3 hours. (During the process, if the solution turns green due to the formation of copper chloride (n), add an appropriate amount of hydroxylamine hydrochloride for reduction.) The solvent is distilled off from the reaction mixture, diluted with 2001 d of water, and 3 d with 100 d of benzene. Extract times. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 6-(3-aminophenyl)-2-methyl-3 was purified by Kagel column chromatography.
, 4.8 g of 5-hexadiyn-2-ol were obtained. This substance was a white crystal.
次に得られたジアセチレン化合物２．４ｇをベンゼン１
００ｍｆｆ１に溶解し、ここに水酸化カリウム粉末０．
３ｇを加え、３時間還流した。室温まで放冷した後、１
００ｍｆｆ１の水で水洗し、有機層を硫酸マグネシウム
で乾燥した後、溶媒を留去、シリカゲルカラムクロマト
グラフィーによりベンゼン、ヘキサン混合溶媒で展開し
精製することにより、１−（３−アミノフェニル）ブタ
ジイン１．１ ｇを得た。このものは白色結晶であった
。Next, 2.4 g of the obtained diacetylene compound was added to 1 part of benzene.
00mff1, and potassium hydroxide powder was added thereto.
3 g was added and refluxed for 3 hours. After cooling to room temperature, 1
After washing with 00mff1 of water and drying the organic layer over magnesium sulfate, the solvent was distilled off, and purified by silica gel column chromatography developed with a mixed solvent of benzene and hexane to obtain 1-(3-aminophenyl)butadiin 1. .1 g was obtained. This substance was a white crystal.
融点 ５３°Ｃ
元素分析値（Ｃ＋ｏｌｌｔＮとして）
計算値（χ）： Ｃ８５，０８，Ｈ５，００，Ｎ ９．
９２実測値（χ）： Ｃ１１４，９７，Ｉ＋ ４．８８
． Ｎ ９．７９実施例５
計雰囲気下、塩化銅（Ｎ １．Ｏｇをエチルアミン７
０％水溶液１５０ＩＩｌに溶解し、ここに２−エチニル
−４，ニトロアニリン１．６ｇをテトラヒドロフラン５
０ｍ１に熔解したものを加え３０分間室温で攪拌する。Melting point 53°C Elemental analysis value (as C+olltN) Calculated value (χ): C85,08, H5,00, N 9.
92 actual value (χ): C114,97,I+ 4.88
．． N 9.79 Example 5 Copper chloride (N 1.0 g) was mixed with ethylamine 7
1.6 g of 2-ethynyl-4, nitroaniline was dissolved in 150 IIl of 0% aqueous solution, and 5 g of tetrahydrofuran was added thereto.
Add the melted material to 0ml and stir at room temperature for 30 minutes.
ここに４−ブロモ−２−メチル−３−ブチン−２−オー
ル１．７ ｇをテトラヒドロフラン３０ｍ１に？容解し
たものを約２時間かけて滴下、以後３時間室温で撹拌す
る。（途中、塩化銅（ＴＩ）の生成により溶液が緑色を
呈した場合、適足のヒドロキシルアミン塩酸塩を加え還
元する。）反応混合物から溶媒を留去し、水２００ｍｆ
ｆ１により希釈しベンゼン１００−により３回抽出する
。有Ｒ層を硫酸ナトリウムで乾燥後、溶媒を留去し、シ
リカゲルカラムクロマトグラフィーにより塩化メチレン
を展開溶媒として分離、精製することにより６−（２−
アミノ−５−ニトロフェニル）−２−メチル−３，５−
へキサジイン−２−オール１゜３５ｇを得た。このもの
は黄色結晶であった。 次に得られたジアセチレン化合
物１．３５ｇをベンゼン１００ｍｆｆ１に溶解し、ここ
に水酸化カリウム粉末２ｇを加え、１０時間還流した。Here, 1.7 g of 4-bromo-2-methyl-3-butyn-2-ol was added to 30 ml of tetrahydrofuran. The dissolved material was added dropwise over about 2 hours, and then stirred at room temperature for 3 hours. (During the process, if the solution turns green due to the formation of copper chloride (TI), add an appropriate amount of hydroxylamine hydrochloride for reduction.) Distill the solvent from the reaction mixture, and add 200 mf of water.
Dilute with f1 and extract three times with 100-benzene. After drying the R layer with sodium sulfate, the solvent was distilled off, and 6-(2-
Amino-5-nitrophenyl)-2-methyl-3,5-
1.35 g of hexadiin-2-ol was obtained. This substance was yellow crystal. Next, 1.35 g of the obtained diacetylene compound was dissolved in 100 mff1 of benzene, 2 g of potassium hydroxide powder was added thereto, and the mixture was refluxed for 10 hours.
室温まで放冷した後、１５０ ｍｌの水で水洗し、有機
層を硫酸マグネシウムで乾燥した後、溶媒を留去、シリ
カゲルカラムク：４．、．１．ｊ。After cooling to room temperature, it was washed with 150 ml of water, the organic layer was dried over magnesium sulfate, the solvent was distilled off, and a silica gel column was added.4. ,． 1. j.
溶媒で展開し精製することにより、１−（２−アミノ−
５−ニトロフェニル）ブタジイン０．８ｇを得た。By developing and purifying with a solvent, 1-(2-amino-
0.8 g of 5-nitrophenyl)butadiine was obtained.
このものは黄色結晶であった。This substance was yellow crystal.
融点１１５℃
元素分析値（Ｃ，。Ｉ（、Ｎ！Ｏ□として）計算値（χ
）： Ｃ６，１，５２，Ｈ３，２５，Ｎ １５．０５実
測値（Ｘ）； Ｃ６４，３８，Ｈ３，０２，Ｎ １５．
２３参考例
前出実施例により得られた本発明に係るフェニルブタジ
イン誘導体の各資料をガラス管に真空封入しコバルト６
０ガンマ−線を用いて固相重合させた。開封後クロロホ
ルム不溶のポリマーの重量から重合収率を求めた。Melting point 115℃ Elemental analysis value (C,. I (, N!O□) Calculated value (χ
): C6,1,52, H3,25, N 15.05 Actual value (X); C64,38, H3,02, N 15.
23 Reference Example Each material of the phenylbutadiine derivative according to the present invention obtained in the previous example was vacuum sealed in a glass tube, and cobalt 6
Solid phase polymerization was carried out using 0 gamma rays. After opening, the polymerization yield was determined from the weight of the chloroform-insoluble polymer.
次表に結果を示した。The results are shown in the table below.
本発明に係るフェニルブタジイン誘導体は、前出実施例
及び参考例に示した通り、置換基がジアセチレン三重結
合と共役する芳香族であり、且つ、非常に高い固相重合
性を有していることにより、非線形光学材料、感光材料
及び高分子半導体材料を形成する為のジアセチレン類の
単量体として好適である。As shown in the preceding examples and reference examples, the phenylbutadiyne derivative according to the present invention has an aromatic substituent conjugated with a diacetylene triple bond, and has extremely high solid phase polymerizability. Therefore, it is suitable as a diacetylene monomer for forming nonlinear optical materials, photosensitive materials, and polymeric semiconductor materials.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5870688A JPH0699372B2 (en) | 1988-03-11 | 1988-03-11 | Phenylbutadiyne derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5870688A JPH0699372B2 (en) | 1988-03-11 | 1988-03-11 | Phenylbutadiyne derivative |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1792794A Division JPH0819054B2 (en) | 1994-01-17 | 1994-01-17 | Phenylbutadiyne derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01233263A true JPH01233263A (en) | 1989-09-19 |
| JPH0699372B2 JPH0699372B2 (en) | 1994-12-07 |
Family
ID=13091947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5870688A Expired - Fee Related JPH0699372B2 (en) | 1988-03-11 | 1988-03-11 | Phenylbutadiyne derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699372B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002170683A (en) * | 2000-04-27 | 2002-06-14 | Fujitsu Ltd | Organic luminescent material and organic electroluminescent element |
-
1988
- 1988-03-11 JP JP5870688A patent/JPH0699372B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002170683A (en) * | 2000-04-27 | 2002-06-14 | Fujitsu Ltd | Organic luminescent material and organic electroluminescent element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699372B2 (en) | 1994-12-07 |
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